Acid-fading inhibition with certain p,p&#39;-diaminodiphenyl-cyclohexane compounds



Patented Jan. 2, [951 ACID-FADING INHIBITION WITH CERTAIN PJ DIAMINODIPHENYL CYCLQHEXANE COMPOUNDS John J. Haydemlioosick Falls, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware N Drawing.

12 Claims.

This invention relates to improvements in the dyeing, of textile materials containing organic derivatives of cellulose (i. e., cellulose esters and ethers, such as cellulose acetate, ethyl cellulose, and the like), whereby the coloratlons thereon are rendered fast to acid fading (also known as atmospheric or gas fading).

Many of .the dyestuffs yielding desirable shades on organic derivatives of cellulose in textile materials, and having satisfactory fastness. to light, washing and other agencies, have been found to be sensitive to fading upon prolonged exposure to acid fumes, particularly the combustion products of coal, gas and other fuels, which are present in minor concehtratLon in the atmosphere, especially in urban communities. In some cases, the brightness of the dyeing is dulled, while in others a marked change in the shade of the coloration occurs. This is especially true of colorations produced with water-insoluble anthraquinone dyes, particularly those yielding valuable blue colorations on organic derivatives of cellulose. When textile materials dyed with those compounds are exposed to acid fumes, the coloration changes to one of a reddish or brownish cast, and on continued exposure may change to a pink coloration. This effect limits to a considerable extent the usefulness of such dyestuffs, which are otherwise highly satisfactory. Sensitivity to acid fumes is not restricted, to anthraquinone dyes, but is likewise noticeable in the case of water-insoluble dyestuffs for organic derivatives of cellulose belonging to other classes.

Numerous proposals have been made to overcome acid fading, ordinarily involving the appli cation to the textile material of compounds or compositions intended to prevent such fading of the coloration. Such compounds or compositions are referred to herein as acid fading inhibitors.

For commercialuse, an acid fading inhibitor should be colorless, having no effect on the shade of the dyestuff produced, adapted to withstand prolonged exposure to light and/or combustion gases without discolo ation, fast to dry cleaning and wet washing, o d rless, and non-toxic in the sense that it causes no skin irritations when materials treated therewith are worn. While most of the acid fading inhibitors heretofore proposed satisfy a number of these requirements, in most cases they are defective in some of said requirements, whereby their usefulness is conslderably impaired. In particular, most of the compounds suggested heretofore are subject to discoloration on exposure to acid fumes and/or to light, so that they cannot be used on goods dyed in light colors or having white designs or backgrounds thereon.

Application December 29, 1948,

Serial No. 68,068

Some of the compounds heretofore employed modify the shade of the dyeing when applied to the material. Many of the proposed compounds or compositions are too soluble in water or in dry cleaning solvents so that they are largely removed When textile materials treated therewith are subjected to customary cleansing treatments.

In addition, from the standpoint of economy and convenience, it is highly desirable that the acid fading inhibitors be applicable to the goods to be dyed together with the water-insoluble dyestufi, so that a separate pre-treatment or aftertreatment with the acid fading inhibitor can be avoided. For this purpose, the compounds employed must have suitable solubility properties, e. g., they are preferably substantially insoluble but dispersible in water; they should be retained in aqueous dispersion under the conditions obtaining in aqueous dyebaths; and they should possess a natural affinity for organic derivatives of cellulose, particularly when applied thereto from aqueous dispersion. While many of the disclosures in the'p-riorart of acid fading inhibitors indicate that they can be applied totextile materials at any time during the processing thereof, including simultaneous application with the dyestuff, many of the suggested compounds tend to separate from the dyebath dispersion at the elevated temperatures often employed for dyeing, forming oily droplets containing the dyestuff which cause spots or streaks on the Inaterial. It is necessary, in order to obtain level application, that the acid fading inhibitor be in solution or dispersion under the conditions of fiber treatment.

I have discovered that certain p,p'-diaminodiphenyl-cyclohexane compounds are highly effective acid fading inhibitors'when applied in minor amounts to textile materials containing organic derivatives of cellulose. These com pounds, employed in accordance with this invention, have the general formula:

represents a cyclohexane ring, Z represents a member 01' the group consisting of hydrogen and I conveniently prepared by condensing 1 mol of cyclohexanone or methyl cyclohexanone with 2 mols of a monocycllc aromatic amine having the formula: I

wherein R and Y have same significance as'defined above, and the position parato the group is unsubstituted. The condensation can be effected by heating a mixture of the aforesaid reagents with an aqueous solution of a strong mineral acid such as hydrochloric or sulfuric acids, at reflux temperature. The reaction product is thereby obtained in the form of an aqueous solution of its acid salt. After separation from any unreacted insoluble material, an excess of alkali is added to precipitate the acid fading inhibitor, which can then be recovered by filtration. Any unreacted aromatic amine can be removed by steam distillation.

The resulting condensation products possess outstanding acid fading inhibiting properties for colorations produced with water-insoluble dyestuifs on organic derivatives of cellulose. They are colorless, substantially insoluble but dispersible in water, possess afllnity for organic derivatives of cellulose materials in textile materials when applied thereto in aqueous dispersion, and yield level dyeings on such materials when applied thereto together with a water-insoluble dyestuif from an aqueous dyebath, containing the acid-fading inhibitor and the dyestufl dispersed therein. When applied to the fiber, they withstand dry cleaning and washing operations without substantial loss in effectiveness. They cause no alteration in the shade of the dyeing on organic derivatives of cellulose as compared with the colorations produced by the dyestufi in their absence. They do not become discolored themselves, and retain their effectiveness during long periods of exposure to light or combustion gases. They cause no irritating or toxic efiect when a fabric to which they have been applied is worn 1 next to the skin. Thus, they possess all of the desired properties required in acid fading inhibitors for the purpose herein specified.

Application of the acid fading inhibitors of my invention to textile materials containing organic derivatives of cellulose may be carried out by treatment of the goods with an aqueous dispersion of the inhibitor before or after the dyeing, but is most conveniently and economically carried out simultaneously with the dyeing. Thus, the inhibitors of this invention can be dispersed in the aqueous bath by any of the methods commonly used for similar dispersion of dyestufis adapted for dyeing organic derivatives of cellulose. For instance, they may be dissolved in a 4 water-miscible solvent and brought into dispersion by means of a dispersing agent having soaplike properties and/or protective colloid action in an aqueous treating bathor dye bath having the desired concentration. Alternatively, the acid fading inhibitor can be solubilized by means of a saponaceous dispersing agent in the same manner as water-insoluble dyestuffs for organic derivatives of cellulose, and the resulting paste added to a treatmentbath or dye bath for the production of dyed textile materials containin organic derivatives of cellulose.

The amount-of acid fading inhibitors of my invention which can be employed may be varied within wide limits, but in general, concentrations in the dye bath of the order of 0.1 to 2%, or more particularly of the order of 1 to 5 times theamount of dyestufi' employed, have been adequate and highly satisfactory, and provide the desired fastness properties in the dyed material.

The temperature of the dye bath may be chosen to suit the dyestuff and the textile material to be dyed. Thus, the dyeing may be carried out at any desired temperature up to -90 C. without injuring the dispersion and without production of spots or streaks.

The following example, wherein parts and percentages are by weight unless otherwise specified, illustrates the preparation and use of the acid fading inhibitors of this invention.

Example 50 parts of cyclohexyl 1,1-bis (p-dimethylamino benzene), prepared by refluxing a mixture of 2 mols of dimethylaniline with 1 mol of cyclohexanone and 2 mols of aqueous 21 Be. hydrochloric acid for 40-50 hours, drowning in dilute aqueous hydrochloric acid at room temperature, filtering out any insoluble material, rendering the filtrate alkaline to phenolphthalein, steam distilling volatile oils from the slurry, and filtering out the insoluble reaction product, are mixed with 50 parts of Igepal C (a higher fatty alcohol-ethylene oxide condensation product). The resulting paste is added in an amount corresponding to 24% of the weight of the material to be dyed, to an aqueous dye bath containing as a dyestuff l-hydroxyethylamino-l-methylamino anthraquinone, in an amount equal to 0.5% of the weight of the material to be dyed. The dyestuif concentration is about 0.2% in the resulting dye bath. Cellulose acetate silk, in the form of yarn or fabric, is worked in the dye bath for about 10 minutes at 71-88 0., then washed with dilute aqueous soap solution, rinsed and dried. A control sample is similarly dyed, except that no acid fading inhibitor is included in the dye bath. A bright blue coloration is produced on both of the samples, which is identical in the case of the control sample and the sample produced with the bath containing the acid fading inhibitor.

The samples are tested for acid fading by exposure to combustion products of illuminating gas for prolonged periods, in accordance with standard testing procedure as described, for example, in the 1946 Yearbook of the American Association of Textile Chemists and Colorists, at pages 285 to 289. The acid fading resistance is rated as set out in the aforesaid handbook in terms of the time required to produce appreciable alteration of shade, the rating units corresponding to about 8 hours exposure to combustion gases. The control sample rapidly changed to a pinkish-blue shade, so that its rating is zero on the aforesaid basis. The rating of the sample' dyed in accordance with this invention shows an acid fading 'resistancerated at 2+.

As a further comparison, cellulose acetate material, dyed in the same manner as the example except that D.l -bis(dimethylamino) diphenylmethane, a compound suggested in the prior art for acid fading inhibition, is employed as the acid fading inhibitor. Comparison of the acid fading resistance of a sample of material thus dyed with the sample dyed according to the example and containing the acid'fading inhibitor of this invention, demonstrated that the material containing the acid fading inhibitor of the prior art changed in shade to a greenish coloration when exposed to combustion products of illuminating gas corresponding to a unit rating of 1, (in the standard testing procedure mentioned above) while the sample prepared with the acid fading inhibitor of the invention remained unchanged in shade under the same conditions.

Other acid fading inhibitors for use in accordance with this invention can be prepared by condensing cyclohexanone with two molecular equivalents of diethylaniline, o-toluidine, aniline, oanisidine, o-phcnetidine and o-chloroaniline. When acid fading inhibitors prepared from'each of these materials were tested in the same manner as described in the example, the resistance of the resulting dyed cellulose acetate material to acid fading was likewise rated as being 2+ units, in each case.

Instead of the foregoing condensation products of cyclohexanone, .the corresponding methylcyclohexanone'condensation products can be used to similar advantage as acid fading inhibitors.

The treatment of fiber or textile material con-- taining organic derivatives of cellulose with the acid fading inhibitors of this invention can be carried out in a manner similar to that described in the example either before or after application of the dyestuif to the textile fiber, and in the same or different baths, to render the dyeing fast to acid fading.

Other saponaceous materials can be used for dispersing the acid fading inhibitor in the fiber treatment bath or dye bath, including for example, sulfonated castor oil, sulfonated mineral oil or castor oil-ethylene oxide condensation products.

The acid fading inhibitors of this invention can be applied singly, or combinations of two or more inhibitors can be used.

Similarly advantageous results are obtained when other water-insoluble dyes for organic derivatives of cellulose of the anthraquinone, azo, or other series, especially dyestuffs yielding a blue coloration and particularly of the anthraquinone series, are substituted for the blue amino anthraquinone dyestuff of the example.

Variations and modifications which will be obvious to those skilled in the art can be made in the foregoing procedural details and compositions without departing from the scope or spirit of the invention.

I claim:

1. A process for increasing the resistance to acid fading of colorations on textile material comprising an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, which comprises incorporating in such material a condensation product of a cyclohexanone with a mono-nuclear aromatic aminefsaid condensation product having the following formula:

represents a cyclohexane ring, Z represents a member of the group consisting of hydrogen and a methyl group, R1 and R2 represent members of the group consisting of hydrogen and lower alkyl groups, and Y represents a member of the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy groups.

2. A process for increasing the resistance to acid fading of colorations on textile material comprising an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, which comprises incorporating in such material a condensation product of cyclohexanone with 2 mols of a lower .dialkylaniline.

3. A process for increasing the resistance to acid fading of colorations on textile material comprising an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, which comprises incorporating in such material a condensation product of cyclohexanone with 2 mols of di methylaniline.

4. A process for increasing the resistance to acid fading of colorations on textile material comprising an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, which comprises incorporating in such material a condensation product of cyclohexanone with 2 mols of diethylaniline.

5. Textile material comprising dyed fibers of an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading having incorporated in said fibers a condensation product of a cyclohexanone with a mono-nuclear aromatic amine, said condensation product having the following formula:

wherein U represents a cyclohexane ring, Z represents a member of the group consisting of hydrogen and a methyl group, R1 and R2 represent members 7 or .the group consisting of hydrogen and lower alkyl groups, and Y represents a member of the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy groups.

6. Textile material comprising dyed fibers of an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading having incorporated in said fibers a condensation product of cyclohexanone with 2 mols of a lower dialkylaniline.

7. Textile material comprising dyed fibers of an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading having incorporatedin said fibers a condensation product of cyclohexanone with 2 mols of dimethylaniline.

8. Textile material comprising dyed fibers of an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading having incorporated in said fibers a condensation product of cyclohexanone with 2 mols of dlethylaniline.

9. In a process for dyeing textile material containing an organic derivative of cellulose of the class consistin of cellulose esters and ethers on which said colorations are normally subject wherein represents a cyclohexane ring, Z represents a member of the group consisting of hydrogen and a methyl group, R1 and R2 represent members of the group consisting of hydrogen and lower alkyl groups. and Y represents a member of the group consisting of hydrogen, halogen, lower aikyl and lower alkoxy groups, and working said textile material in the resulting bath until dyeing is complete.

10. In a process lor dyeing textile material containing an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, the improvement which comprises dispersing, in a dye bath containing a water-insoluble dyestufi for said textile material, a condensation product of cyclohexanone with 2 mols oi a'lower dialkylaniline, and working said textile material in the resulting bath until dyeing is complete. Y

11. in a process for dyeing textile material containing an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, the improvement which comprises dispersing, in a dye bath containing a water-insoluble dyestuff for said textile material, a condensation product of cyclohexanone with 2 mols of dimethylaniline, and working said textile material in the resulting bath until dyeing is complete.

12. In a process for dyeing textile material containing an organic derivative of cellulose of the class consisting of cellulose esters and ethers on which said colorations are normally subject to acid fading, the improvement which comprises dispersing, in a dye bath containing a water-insoluble dyestuff for said textile material, a condensation produce of cyclohexanone with 2 mols of diethylaniline, and working said textile material in the resulting bath until dyeing is complete.

JOHN J. HAYDEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,914,945 Ellis June 20, 1933 1,930,232 Ellis Oct. 10, 1933 2,083,122 Olpin June 8, 1937 2,094,809 Olpin Oct. 5, 1937 2,255,090 Tinker Sept. 9, 1941 2,369,122 Giles Feb. 13, 1945 

2. A PROCESS FOR INCREASING THE RESISTANCE TO ACID FADING OF COLORATIONS ON TEXTILE MATERIAL COMPRISING AN ORGANIC DERIVATIVE OF CELLULOSE OF THE CLASS CONSISTING OF CELLULOSE ESTERS AND ETHERS ON WHICH SAID COLORATIONS ARE NORMALLY SUBJECT TO ACID FADING, WHICH COMPRISES INCORPORATING IN SUCH MATERIAL A CONDENSATION PRODUCT OF CYCLOHEXANONE WITH 2 MOLS OF A LOWER DIALKYLANILINE. 